CN103708494A - Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve - Google Patents
Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve Download PDFInfo
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- CN103708494A CN103708494A CN201310744075.6A CN201310744075A CN103708494A CN 103708494 A CN103708494 A CN 103708494A CN 201310744075 A CN201310744075 A CN 201310744075A CN 103708494 A CN103708494 A CN 103708494A
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Abstract
The invention relates to a novel modification method of a titanium silicalite molecular sieve. The method comprises the following operating steps: 1, adding a titanium silicalite molecular sieve to a mixed aqueous solution containing metal salt and an acid solution to obtain a mixture in which the mole ratio of the titanium silicalite molecular sieve to the metal salt to the acid to the water of 0.01:(0.005-5):(0.001-3):(1-100); 2, crystallizing the mixture obtained in the step 1 for 3-72 hours at the temperature of 60-150 DEG C; and 3, washing, drying and roasting to obtain the modified titanium silicalite molecular sieve. The method disclosed by the invention has the beneficial effects that the method has universal applicability and is particularly suitable for titanium silicalite molecular sieves synthetized by using a classical method; and when being applied to cyclohexanone ammoximation reactions, the modified titanium silicalite molecular sieve obtained through the method disclosed by the invention has the advantages that the reaction performance is increased greatly, and the service life of a catalyst is prolonged.
Description
Technical field
The invention belongs to molecular sieve catalytic Material Field, relate to particularly a kind of method of modifying and application thereof of novel titanosilicate.
Background technology
HTS is that transition metal titanium is introduced and had a kind of novel titanosilicate with good selective paraffin oxidation catalytic performance forming in the framework of molecular sieve of ZSM-5 structure.It not only has the catalysed oxidn of titanium, and has the shape effect selected and the good stability of ZSM-5, has good oxidisability and specific selectivity.The green catalysis system that particularly TS-1 and hydrogen peroxide form, has avoided the problem of complex process and contaminate environment, has good prospects for commercial application.Be widely used at present in the organic oxidizing reactions such as phenol, alcohols, ethers, and cyclohexanone oxamidinating and epoxidation of propylene etc. have been realized suitability for industrialized production.
Current synthetic about HTS, classical method is that to adopt respectively tetraethoxy and organic titanium fat be He Tai source, silicon source, the TPAOH of take is carried out Hydrothermal Synthesis as template under certain temperature and pressure.But in above building-up process, because the hydrolytic process of organic silicone grease and organic titanium fat is wayward, hydrolysis rate is difficult to coupling, thus be very easy to form extra-framework titanium species, and TS-1 is had a negative impact.First extra-framework titanium itself does not have catalytic oxidation activity but can cause a large amount of decomposition of hydrogen peroxide, causes thus the reduction of TS-1 catalytic performance; Secondly, the content of extra-framework titanium is unmanageable, and this causes the activity stability of HTS poor, has so restricted the industrial application of TS-1.
Patent CN1268400A has proposed a kind of aqueous solution of metal-salt or other mixtures that utilizes and TS-1 has been carried out to the method for modification, it is characterized in that the aqueous solution of metal-salt and TS-1 to mix by a certain percentage, at 30-100 ℃, react 6-100h, then dry at 110-200 ℃, then temperature programming is to 200-800 ℃, roasting 2-20h.By the HTS of this method modification, for epoxidation of propylene, have good effect, but effect is general in cyclohexanone oxamidinating, the performance of the molecular sieve that is not significantly improved.
A kind of preparation method of sour modifying titanium-silicon molecular sieve has been proposed in patent CN1657168A, it is characterized in that TS-1 molecular screen primary powder, the acidic cpd of not roasting to mix, be considered as carrying out sour modification at-200 ℃, filter, obtain calculating after washing, dry, roasting the TS-1 molecular sieve of modification.The method is simple to operate, can effectively haul out the extra-framework titanium species in molecular sieve, and the transformation efficiency of HTS is increased, but selectivity changes not quite.
Summary of the invention
The present invention will solve the problems of the technologies described above, and a kind of method of modifying of novel titanosilicate is provided, and is especially applicable to the synthetic TS-1 molecular sieve of classical formalism, can improve transformation efficiency, selectivity and the life-span of TS-1 catalysis of pimelinketone oxamidine reaction.
The concrete technical scheme adopting is as follows:
A method of modifying for novel titanosilicate, operation steps is:
Step 1: HTS is added in the mixed aqueous solution that contains metal-salt and acid solution, and obtaining mol ratio is HTS: metal-salt: acid: water=0.01:(0.005～5): (0.001～3): the mixture of (1～100);
Step 2: the mixture that step 1 is obtained crystallization at 60～150 ℃ is processed 3～72h;
Step 3: then wash, be dried, roasting, obtain the HTS after modification.
In described step 1, acid solution used is organic acid compound.
Described organic acid compound is that structure is R(COOH) lipid acid of n, wherein R is the alkyl with 1～4 carbon atom, n=1～2.
In described step 1, acid solution used is mineral acid.
Described mineral acid is one or more in hydrochloric acid, hydrofluoric acid, phosphoric acid, sulfuric acid, nitric acid.
Described metal-salt is one or more the mixture in metal nitrate, metal acetate salt, metal ammonium salt.
Described metal-salt is one or more the mixture in SODIUMNITRATE, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Described in step 3, drying temperature is 80～150 ℃, and be 1～15h time of drying.
Described in step 3, the temperature of roasting is 350 ℃～600 ℃, and roasting time is 2～15h.
Molecular sieve after modification is for cyclohexanone oxamidinating reaction.
Use in the present invention mineral acid to remove the extra-framework titanium species and the hydrophilic and hydrophobic that changes HTS surface in HTS by while effective as selective, the catalytic oxidation activity that obtains the HTS of modification increases substantially.Especially use one or more effects in hydrochloric acid, hydrofluoric acid, phosphoric acid, sulfuric acid, nitric acid more obvious.
The metal-salt using in the present invention is by the interaction of metal oxide and HTS, can make the activity of molecular sieve be improved, the selectivity that not only can improve the active of HTS but also can improve pimelinketone in cyclohexanone oxamidinating reaction by changing the consumption of metal oxide.Especially use one or more the mixture effect in metal nitrate, metal acetate salt, metal ammonium salt more obvious.
The invention has the beneficial effects as follows: the present invention has general applicability, be particularly useful for the synthetic HTS of classical way, HTS after the modification obtaining by the present invention is reacted for cyclohexanone oxamidinating, and reactivity worth increases substantially, and has improved the life-span of catalyzer.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below the specific embodiment of the present invention is described further, but does not limit protection scope of the present invention.
First, the HTS that each embodiment is used makes by classical hydrothermal synthesis method, by TPAOH, do that template, tetraethoxy are done silicon source, butyl (tetra) titanate is done titanium source, reactant mole consists of: tetraethoxy: butyl (tetra) titanate: TPAOH: Virahol=1:0.01～0.3:0.1～0.5:30～60 preparation molecular sieve mother liquor, then crystallization 15～96h at 120～190 ℃ in autoclave, filters, obtains HTS after washing, dry, roasting.
Embodiment 1
By the HTS making with aforesaid method for modification, according to HTS: SODIUMNITRATE: hydrochloric acid: water mol ratio=0.01:0.005:0.001:1 prepares mixing solutions, 60 ℃ of reaction 72h, washing, 80 ℃ of dry 15h, 350 ℃ of roasting 15h, obtain molecular sieve after modification.
Embodiment 2
By the HTS making with aforesaid method for modification, according to HTS: nickelous nitrate: nitric acid: water mol ratio=0.01:5:3:100 prepares mixing solutions, 150 ℃ of reaction 3h, washing, 150 ℃ of dry 1h, 600 ℃ of roasting 2h, obtain molecular sieve after modification.
Embodiment 3
By the HTS making with aforesaid method for modification, according to HTS: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: phosphoric acid: water mol ratio=0.01:2:0.5:50 prepares mixing solutions, 80 ℃ of reaction 48h, washing, 140 ℃ of dry 10h, 500 ℃ of roasting 8h, obtain molecular sieve after modification.
Embodiment 4
By the HTS making with aforesaid method for modification, according to HTS: sodium-acetate: hydrofluoric acid: water mol ratio=0.01:0.5:0.5:75 prepares mixing solutions, 90 ℃ of reaction 10h, washing, 100 ℃ of dry 12h, 450 ℃ of roasting 10h, obtain molecular sieve after modification.
Embodiment 5
By the HTS making with aforesaid method for modification, according to HTS: nickelous nitrate: sulfuric acid: water mol ratio=0.01:0.5:0.3:80 prepares mixing solutions, 130 ℃ of reaction 64h, washing, 110 ℃ of dry 10h, 550 ℃ of roasting 4h, obtain molecular sieve after modification.
Embodiment 6
By the HTS making with aforesaid method for modification, according to HTS: SODIUMNITRATE: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES: hydrochloric acid: water mol ratio=0.01:0.5:0.5:1:50 prepares mixing solutions, 120 ℃ of reaction 36h, washing, 90 ℃ of dry 13h, 500 ℃ of roasting 10h, obtain molecular sieve after modification.
The modifying titanium-silicon molecular sieve that above-mentioned unmodified HTS and embodiment are obtained reacts for cyclohexanone oxamidinating, catalyst performance relatively, and concrete grammar is as follows:
80 ℃ of water-baths, in airtight there-necked flask, add the 50ml trimethyl carbinol, 8g pimelinketone, 15g25% ammoniacal liquor, 2gTS-1,10g hydrogen peroxide slowly adds with micro-sampling pump, reacts after one hour Agilent 7890 transformation efficiencys of chromatographic determination pimelinketone and the selectivity of cyclohexanone-oxime for the product obtaining.
Wherein, amount * 100% of the pimelinketone of pimelinketone transformation efficiency=(amount of the amount of the pimelinketone adding-remaining pimelinketone)/add;
Amount * 100% of the pimelinketone of pimelinketone amount/conversion that cyclohexanone-oxime selectivity=change into cyclohexanone-oxime consumes.
Concrete analysis result following table is carried out comparative illustration:
| ? | Transformation efficiency/% | Selectivity/% |
| Unmodified | 88.5 | 98.2 |
| Embodiment 1 | 92.5 | 98.9 |
| Embodiment 2 | 93.3 | 99.2 |
| Embodiment 3 | 94.6 | 98.9 |
| Embodiment 4 | 95.7 | 99.1 |
| Embodiment 5 | 96.5 | 99.4 |
| Embodiment 6 | 97.2 | 99.2 |
By upper table result, can find out, through the HTS of this method modification, in transformation efficiency and the selectivity of cyclohexanone oxamidinating reacting middle catalyst, be improved significantly,
Method of modifying of the present invention and purposes are described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (10)
1. a method of modifying for novel titanosilicate, is characterized in that, operation steps is:
Step 1: HTS is added in the mixed aqueous solution that contains metal-salt and acid solution, and obtaining mol ratio is HTS: metal-salt: acid: water=0.01:(0.005～5): (0.001～3): the mixture of (1～100);
Step 2: the mixture that step 1 is obtained crystallization at 60～150 ℃ is processed 3～72h;
Step 3: then wash, be dried, roasting, obtain the HTS after modification.
2. a kind of method of modifying of novel titanosilicate according to claim 1, is characterized in that, in described step 1, acid solution used is organic acid compound.
3. a kind of method of modifying of novel titanosilicate according to claim 2, is characterized in that, described organic acid compound is that structure is R(COOH) lipid acid of n, wherein R is the alkyl with 1～4 carbon atom, n=1～2.
4. a kind of method of modifying of novel titanosilicate according to claim 1, is characterized in that, in described step 1, acid solution used is mineral acid.
5. a kind of method of modifying of novel titanosilicate according to claim 4, is characterized in that, described mineral acid is one or more in hydrochloric acid, hydrofluoric acid, phosphoric acid, sulfuric acid, nitric acid.
6. a kind of method of modifying of novel titanosilicate according to claim 1, is characterized in that, described metal-salt is one or more the mixture in metal nitrate, metal acetate salt, metal ammonium salt.
7. a kind of method of modifying of novel titanosilicate according to claim 6, is characterized in that, described metal-salt is one or more the mixture in SODIUMNITRATE, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
8. a kind of method of modifying of novel titanosilicate according to claim 1, is characterized in that, drying temperature is 80～150 ℃ described in step 3, and be 1～15h time of drying.
9. a kind of method of modifying of novel titanosilicate according to claim 1, is characterized in that, the temperature of roasting is 350 ℃～600 ℃ described in step 3, and roasting time is 2～15h.
10. the HTS that a kind of method of modifying of novel titanosilicate makes according to claim 1, is characterized in that, for cyclohexanone oxamidinating, reacts.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528758A (en) * | 2014-12-22 | 2015-04-22 | 中国天辰工程有限公司 | Aftertreatment method of TS-1 titanium silicalite molecular sieve |
| CN105728035A (en) * | 2016-03-17 | 2016-07-06 | 中国天辰工程有限公司 | Method for regenerating deactivated catalysts for liquid-phase cyclohexanone ammoximation technology |
| CN105921171A (en) * | 2016-04-29 | 2016-09-07 | 山西大学 | Method for improving stability of cyclohexanone ammoximation catalyst TS-1 molecular sieves |
| CN107308982A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane |
| WO2018088436A1 (en) * | 2016-11-11 | 2018-05-17 | Ube Industries, Ltd. | Ammoxmation catalyst and process for producing oxime |
| CN110252394A (en) * | 2019-07-18 | 2019-09-20 | 北京赛诺时飞石化科技有限公司 | A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN112591762A (en) * | 2020-12-14 | 2021-04-02 | 湖南化工职业技术学院（湖南工业高级技工学校） | Ultrasonic-assisted titanium-silicon molecular sieve modification method |
| CN115872896A (en) * | 2022-12-05 | 2023-03-31 | 衢州巨化锦纶有限责任公司 | Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve |
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| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
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| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| CN1657168A (en) * | 2004-12-09 | 2005-08-24 | 华东师范大学 | Preparation method of acid modified titanium-containing molecular sieve |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528758A (en) * | 2014-12-22 | 2015-04-22 | 中国天辰工程有限公司 | Aftertreatment method of TS-1 titanium silicalite molecular sieve |
| CN104528758B (en) * | 2014-12-22 | 2017-04-05 | 中国天辰工程有限公司 | A kind of post-processing approach of 1 HTSs of TS |
| CN105728035A (en) * | 2016-03-17 | 2016-07-06 | 中国天辰工程有限公司 | Method for regenerating deactivated catalysts for liquid-phase cyclohexanone ammoximation technology |
| CN105728035B (en) * | 2016-03-17 | 2018-10-09 | 中国天辰工程有限公司 | A kind of liquid phase cyclohexanone oxamidinating technique decaying catalyst regeneration method |
| CN107308982A (en) * | 2016-04-26 | 2017-11-03 | 中国石油化工股份有限公司 | The synthetic method of modifying titanium-silicon molecular sieve catalyst and its preparation method and application and epoxychloropropane |
| CN105921171A (en) * | 2016-04-29 | 2016-09-07 | 山西大学 | Method for improving stability of cyclohexanone ammoximation catalyst TS-1 molecular sieves |
| CN105921171B (en) * | 2016-04-29 | 2018-07-24 | 山西大学 | A method of improving cyclohexanone oxamidinating catalyst TS-1 molecular sieve stability |
| WO2018088436A1 (en) * | 2016-11-11 | 2018-05-17 | Ube Industries, Ltd. | Ammoxmation catalyst and process for producing oxime |
| CN110252394A (en) * | 2019-07-18 | 2019-09-20 | 北京赛诺时飞石化科技有限公司 | A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation |
| CN110372536A (en) * | 2019-08-15 | 2019-10-25 | 中触媒新材料股份有限公司 | A kind of method of preparing cyclohexanone oxime by ammoximation of cyclohexanone |
| CN112591762A (en) * | 2020-12-14 | 2021-04-02 | 湖南化工职业技术学院（湖南工业高级技工学校） | Ultrasonic-assisted titanium-silicon molecular sieve modification method |
| CN115872896A (en) * | 2022-12-05 | 2023-03-31 | 衢州巨化锦纶有限责任公司 | Preparation method for producing butanone oxime by using nickel-doped titanium silicalite molecular sieve |
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